Separation of hydrocarbons



Feb. 8, 1949. J. A. PATTERSON SEPARATION oF HYDRodARBoNs 2 sheet-sheet 1 KNSQNR mN Il www Nlwumuw Feb. 8, 1949. 1 A, PATTERSQN 2,461,346

SEPARATION 0F HYDROCARBONS Filed Dec. 28, 1944 2 Sheets-Sheet 2 :KEW Nm rSM l a Hnmwhl KQQKN A .hm

kbukwk rauh' a ,5S mww MQ NW n Patented Feb. 8, 1949 .K 2,461,346 l SEPARATION or nYnnocannoNs John A. retienen, Beverly,v N. J., assigner' te Standard Oil Development Company, a corporation of Delaware Appui-.ation neeembeias, 1944, sei-lai 570,193

1 Y This invention relates to th separation of constituents of complex hydrocarbon -mixtures by .solvent distillation. It relates particularly to the maintenance of desired solvent purity by the extraction from solvent concentrates of h igh boiling compounds, particularly dicyclopentadiene, formed in the course of processing to separate dioieflns from admixture with monooleilns and paraillns of about the same boiling range.

Hydrocarbons diillcult to separate from complex mixtures by ordinary distillation can often be separated by vapor phase extraction or extractive distillation. In such processing, a selective solvent for one or a relatedseries of compounds is passed down a fractionation tower. In the pres- .ence of the solvent, the hydrocarbons selectively 'q'uently Aundergo deterioration, especially polymerization.' to form liquid and solid4 complexes which normally concentrate in the solvent.

f 'the polymers so produced, the formation of 'the liquid compounds is not substantially reduced fby the addition of inhibitors effective in checking 1 Claim. (Cl. Zim- 6815) tion.

' 2 advantage is attained without the use of any additional water-scrubbing equipment overthat required to treat the various extractive fractions.

The present invention thus relates to a method of removing the liquid polymers and, as a feature of processing, the maintenance of liquid polymer concentration in the solvent below the level at which a disadvantageous processing eiIect isencountered. V l

It is an object, therefore, of the invention to effect separation of individual compounds from complex hydrocarbon mixtures, especially of the Cs hydrocarbons, by processing involving solvent distillation made particularly advantageous by reason of maintaining satisfactory solvent purity and a continuous elimination of high boiling polymers which are the source of solvent contamina- Other objects will be apparent from the following description and illustration of the linthe formation of lthe more complex solid compounds.l The high boiling polymers, being soluble in' the solvent, reduce its selectivity, complicate `process control and add mechanical difiiculties, especially as to theoperatio'n of heat ex- :changers and valves. ,"llquid polymers from-the solvent by distillation The separation of these is furthermore complicated by reason of the for- 'mation of azeotropes. In commercial processing,

these adverse effects must be obviated or minimized to permit good processing. In the extractive distillation of narrow boiling petroleum distillates to obtain selectively the Cs hydrocarbons, the solvent forms azeotropic mixtures with the olefin and residual Cs fractions.

Water washing of the solvent extracts furnishes :a practical and convenient method of separating -the hydrocarbons from these solutions and also of recovering the solvent itself. However, when bleed fraction, however, extraction of the solvent be made withoutx emulsion difficulties. This vention.

Thus, in the extractive distillation process for lthe separation of lsoprene from refinery cracked stocks, it has been found that dicyclopentadiene is the main constituent of 'the liquid polymeric material. This dimer occurs in substantial proportions in the solvent after stripping, and, unless immediately removed, is recycled to the extracvto the waterextractor. In the purlcation of Cs diolens, the present invention nds particularly advantageous application. The solvent bleed is mixed with spent Csfraction azeotropic mixtures before it enters the'water scrubber and polymer from the solvent leaves the system in the spent Cs cut. The dilute acetone solution'in water is combined with the similar solution from the C5 diolen water scrubber and the acetone is recovered by distillation from the combined stream. The water content of the solvent in the system can thus be adjusted by varying. the content of water in the overhead from the solvent distillation tower. A i l Y The liquid polymeric material, largely dicyclopentadiene, is also present in substantial amounts in the nal fractionator bottoms.` Usually the dicyclopentadiene isv discarded because the concentrations in the stripped solvent and in the .ilnal fractionator bottoms lare too' small to justify recovery. These rejections of dicyclopentadiene are losses from the comercial viewpoint since the material is important in the preparation of plastics. It is an added feature, therefore, of this invention to combine these sources ordicyclopentadiene and to recover this compound. The invention is therefore concerned, in the processing with regard to the Cs hydrocarbons, with the removal of liquid polymeric materials in the segregatlon and purification of the respective paraiiins and oleiins, and at the same time recovering the valuable commercial product, dicyclopentadiene.

The invention in regard to the separation and purification of isoprene .from renery cracked stocks and recovery of dicyclopentadiene finds embodiment in combining a portion of the recycle solvent stock from the extractive distillation unit with the product fractionator bottoms and then water-washing the combined streams vto remove the contained solvent. The Cs hydrocarbons are then separated from the polymeric material by steam stripping. By such processing, essentially all of the polymer, mainly dicyclopentadlene, in the system for the separation and recovery of dioletln hydrocarbons from complex hydrocarbon mixtures is obtained in concentrated form. By such processing, therefore, dicyclopentadiene becomes a by-product in the process for the separation and purification of individual Cs hydrocarbons from complex petroleum mixtures.

In order to present a detailed understanding of the invention, the following description of processing is presented. The reference numeralsA given in the description refer to the accompanying drawing. In this drawing a suitable layout of equipment and indication of a suitable flow of materials for processing according to the invention are presented. In the illustration, example will be taken of the separation and puriilcation of isoprene by the treatment of a close boiling fraction of composition:

obtained as a distillate from a debutanized distillate from the vapor phase steam cracking of a virgin gas oil.

This hydrocarbon mixture is passed to an extractiva distillation tower Il in which a liquid solvent is employed to yield vapor and liquid fractions. This extractive distillation may be carried out in any of the usual forms of fractionating equipment, such as a tower illled with packing oi refractory materials or a tower constructed in the same manner as an ordinary fractionating tower of the bubble cap type. Usually the feed enters the tower as a vapor for reasons of economy and is then passed upwardly through the liquid phase selective solvent flowing down the tower.

In the tower, plate conditions are such that the liquid mixtures of close boiling hydrocarbons and solvents are at their boiling points and are continuously being contacted with the vapors rising upwards from the plates beneath. On account of the low volatility of. the solvent relative to that of the hydrocarbon the vapors are poorer in solvent constituents and rich in the hydrocarbon compounds. By maintaining the quantity of soivent circulated to the tower constant or in a definite ratio to the amount of 4overhead to thee tower, optimum conditions for the separation of hydrocarbons can be achieved. Also by controlling the amount of hydrocarbon reilux and conse- .quently the reflux ratio, the degree of fractionaprocessing according to the invention, about 09 plates are present in such a tower. The tower is shown as being complete with an overhead vapor line I2, a condenser I3, a drum I4, a reflux line I5, a bottoms line II, a reboiler I3 and a reboiler vapor line I9. The tower has also a solvent line 39, a side stream vapor line 3i and a side stream return line 36. The distillate product is withdrawn from the system through line 4I and the bottoms product through line I1. Pressure upon the system is maintained at about 25 lbs. per sq. in. (gauge), in order to have a workable condensing temperature.

The overhead distillate vapor removed through line I2 consists of azeotropic mixtures of Csoleflns and paraiiins when aqueous acetone is employed as the solvent material admitted through line 39. The vapors are condensed in equipment I3 and passed to the reilux drum I4. A portion of the condensate is returned through line I5 as reflux, while the remainder is withdrawn through line l I cooled in equipment 42 and conducted through line 43 to the water scrubbing equipment 50.

The quantity of aqueous acetone admitted through line 39 to the distillation system is for the specific composition of feed stock in a volume ratio of solvent to hydrocarbon mixture of 2-1 from the point of introduction to the plate upon which the side stream is withdrawn. Below the plate from which the side stream product is withdrawn, the solvent is stripped of its hydrocarbon content.

The bottoms withdrawn through line I6 consist of relatively pure solvent. A portion of the bottoms liquid is passed through the reboiler Il where it is vaporized, the vapors being returned to the tower III through the vapor line I9, to supply the heat necessary to operate the tower. The remainder of the solvent, except for a small portion withdrawn for purification, as to be further described, is conducted through line I1 to cooler 38 and then through line 39 to the upper portion of the tower I0. Thus, the major part of the solvent contnuously recycles within the extractive distillation system.

The vapor side stream removed through line 3| contains a high concentration of isoprene with small amounts of other dioleflns in the presence of solvent in an amount in equilibrium with a molar per cent concentration of solvent on the plates of the extractive distillation tower I0. The volume of the solvent is about 50% of the vapor mixture. This side stream material withdrawn through line 3i is conducted to the base of the side stream concentrating tower 30. The tower il may be any suitable iractionating` apparatus, such as a tower provided with bubble plates, as previously employed. The tower is provided with an overhead vapor line 32. a condenser I3, a retion. The vapor is condensed in equipment 33 and conducted to the drum 3l. A portion of the condensate is returned to the tower through line as reflux, while the remainder ls withdrawn through line 31 to the water scrubbing equipment l0.

The degree of separation of the hydrocarbons taking place in the extractive distillation system il is dependent on two functions, namely, the ratio of the solvent to hydrocarbon liquid on the plates and the ratio of liquid to vapor owing through the tower. The ratio of solvent to hydrocarbon is controlled by the rate of solvent recirculation. The ratio of liquid to vapor in the zone of high solvent to hydrocarbon ratio, that is, between the solvent inlet and the side stream outlet, is controlled by the reflux returned through line Il from the reflux drum Il. Due to considerable din'erence in solvent concentration between the top of the tower and the extractive rdistillation zone and the difference in latent heats of the constituents, the reux ratio and consequently the ratio of liquid to vapor at the top of the tower must be appreciably higher than the liquid to vapor ratio in the extractive distillation zone.

In the case of the specic example, the liquid to vapor ratio in the extractive distillation zone is 0.80, while the ratio at the top of the tower is 0.85, the latter being equivalent to a reux ratio of 5.5. The reiiux ratio used in the side stream tower 30 is adjusted so as to obtain an overhead product consisting essentially of the azeotropic mixture of isoprene, acetone and Water and to supply adequate reflux to the solvent stripping section of the tower l0. Whichever requires the larger amount of 'redux determines the reflux ratio at the top of the tower 30. In the case cited in the example, a reilux ratio of 20 is maintained at the top of the tower 30, in order to supply adequate reux to the bottoms solvent stripping section of the tower I0.

The heat necessary for` the extractive distillation operation, as well as to concentrate the hydrocarbon fractions and to` strip the solvent, is supplied completely from the single reboiler l0. In this manner, considerable heat economy is efected. since the heat to operate the extractive distillation zone in tower I0 and the diolefln concentrating side stream tower 30 are supplied by condensation of solvent at -the top of the solvent stripping section of the tower. If this were not done, a condenser would have to be provided for the solvent stripper to supply the reilux necessary for operation, and additional heat would be required to operate the extractive distillation system and to effect the side stream concentration. In the same way. the condensation needed to produce the required reux in the extractive distillation zone is obtained by supplying the heat needed to concentrate the monooleflns at the top of the tower I0.

' of the materials passing through it.` The stream.v

Inl e operation of the :systeml comprising towe Il and I0 and theirvauxiliaries. separation into the zones indicated above is clearly donned by the various temperature zones. Thus. the vapor leaving the top of thetower Il is at l". The temperature rises sharply to F. between the top of the tower and the plate on which tl'ie` solvent is admitted through line I0, then very slowly reaching to F. at the plate where the side stream is withdrawn through line 3L Below.

removed as distillate from the tower 30 through line 32 is conducted to the water scrubbing equipment 40. Equipment I0 may be any suitable type of a .liquid-liquid contacting device, in which countercurrent iiow of the materials may be maintained. In the present case, the tower is packed with- Raschig rings and suilicient pressure is main-- tained on the tower .to prevent vaporization of'any removed from the system through-.linel 31 is admitted to the bottom of the tower 40 through a distributing deviceand then allowed to flow upward countercurrent to a stream of water admitted to the tower through line M.

`In passing through the tower, the acetone is removed andthe hydrocarbonis thus completely freed of the solvent employed in the extractive distillation. The quantity of water employed is determined by the partition of the solvent between the hydrocarbon and the water and the emciency of the extracting equipment Il; For the specific 4composition chosen, a volume ratio of water to distillateis approximately 1. Passing overhead from the tower is partially purified isoprene in a high concentration. Impurities present in the stream consist of plperylene, cyclopentadiene, polymers and any other water-insoluble materials contained in the distillate from4 the tower 30. The water extract removed from the tower through line 40 consists of a dilute solutionk tower containing 50 bubble cap plates -is em.

ployed. The tower 10 is provided with an overhead vapor line 12, a. condenser 13, a reux drum 14, a reflux line 15 and a bottoms withdrawal line 18, a reboiler 18 and a reboiler vapor return line 19. The distillate product is withdrawn through line 8| and the bottoms product through line 11. Pressure is maintained on the` system so as to effect satisfactory condensation with-ordinary water in the condenser 13. In `the specic example, pressure maintained upon the tower 10 is vbetween 12 and 15 lbs. per sq. in. (gauge).

The distillate withdrawn through line 12 consists of highly purified isoprene containing traces of piperlyene and pentenes. The distillate is condensed in equipment 1l and the condensate the vapors being returned to the tower through line 19 to supply the heat necessary to operate the tower. The remainder of the bottoms are removed through line Il and passed through line 9|. Into line 9| is also passed about 5% of the solvent withdrawn from the base of the extraction tower l0.

Equipment 90 may be any suitable type of liquid-liquid contacting device in which countercurrent ilow of materials may be maintained. The tower in the present case is packed with Raschig rings and sufllcient pressure is maintained therein to prevent vaporization of any of the materials passing through the tower. The

stream passes through line 9| and is admitted to the bottom of the tower 90 through a distributing device and then allowed to flow upward countercurrently to the stream of water admitted to the tower through line 94. In passing through the tower, the acetone is dissolved and thus the polymer is removed from solution. The quantity of water employed is determined by the partition of the solvent between the water and the polymer and the efllciency of the contacting devices in the extracting equipment 90. For the specific composition of this invention, a volume ratio of water to distillate of approximately 1 is maintained.

The water extract removed from the tower 90 through line 93 consists of a dilute solution of acetone and water. This extract is combined with the other dilute solutions of acetone from the towers 40 and 50 and passed through heat exchanger 52 prior to passingto the tower 60 for the recovery of the acetone content.

The polymer in high concentration passes overhead from the tower 90 through line 92. Impurities present in this stream consist of cyclopentadiene and cyciopentene and any water-insoluble materials contained in the streams from towers l0 and 10. This stream passes through heat exchanger |06, through line |06, to distillation tower |00. The tower |00is equipped with overhead vapor line |02, a condenser |03, a drum |04, a reflux line |05, a bottoms line |06 and a steam inlet line |01. The heat required to operate the tower is obtained by the passage of open steam through line |01. Taken overhead through line |02 are the impurities associated with the polymer. This stream is condensed in equipment |03 and collected in the drum |04. A portion of this condensate is returned to the tower |00 as reflux through line |05, while the remainder is passed through line ||0 to be treated as desired for the recovery of any of the particular compounds. The polymer in high degree of purity isV removed as the distillation residue through line |06, passed through heat exchanger |08 and thence through line |01 for collection as desired.

By increasing the number of plates in tower 10 or increasing the retlux ratio, all of the isoprene may be taken overhead as purified product. l It has been found, however, more emcient to reject a small amount of isoprene to the bottoms and recycle same for recovery as described. A reflux ratio of I2 is maintained for the desired separation in the tower 10.

The distillate fraction from the tower I0 which is withdrawn throughline 4|, containing the azeotropic mixtures of the C5 paraftlns and olefins, is cooled `in equipment 42 and conveyed through line 43 to the extraction tower 50. The extraction tower 50 is similar to the extraction tower 40. It is similarly packed with Raschig rings. The composite solution consisting of the Cs olefins andV parafns, in addition to acetone and water, is introduced into the tower 60 near the bottom and passes upward through the tower countercurrently to a stream of water introduced near the top through line 45.

In passing through the tower, the solvent is extracted from the hydrocarbon material. The hydrocarbons freed of solvent are removed through line 4l at the top of the tower 60 and discarded. The water extract consisting of a dilute solution of acetone in water is withdrawn through line 49A at the bottom of the tower 50 and after being combined with similar extracts from the towers 40 and S0 is transferred through line 5|, through heat exchanger 52 and line 6| to the solvent recovery tower 60.

Tower 60 may be any convenient device for effecting fractional distillation. such as a tower containing about ,20 bubble cap plates. It is provided with an overhead vapor line 62, a condenser 63, a reflux drum 64, reflux line 65, a bottoms withdrawal line 66 and a steam line 68. The distillate product is withdrawn through line 60 and `the bottoms through line 61. The distillate from the tower 60 consists'of relatively pure solvent. The tower is operated at about atmospheric pressure. The distillate vapor passes through line 62 to the condenser 63 and the condensate passed to reflux drum 64. A portion of the condensate is returned to the tower 60 through line 65, while the remainder is withdrawn and transierred through line 69 to line 39 where it combines with the solvent admitted to the tower 20. Heat is supplied to the tower 60 by means of a steam line 68 through which open steam is injected directly into the bottom of the tower. The bottoms comprising the major part of the water content of the feed and the condensed steam are withdrawn through line 66 to the heat exchanger 52. The heat exchanger 52 is also utilized to heat the feed to the tower B0. Thus, the sensible heat of the bottoms is utilized.

The reux returned to the tower 60 through line 65 is controlled at such a rate that the water content of the distillate passing through line 62 and consequently the product returned to the tower 30 through lines 69 and 39 is the saine as the recycled solvent in tower 30. By proper adjustment of the reflux ratio in tower 60, the water content of the product may be varied to correct the variations in the water content of the solvent in the tower 30. Normally a reflux ratio of about 0.5 is maintained in the tower 60.

With the foregoing disclosure and illustration of the invention it will be obvious to those skilled in the art that various combinations and variations of the applications of the principles described and illustrated can be made without departing from the inventive concept and that the invention i in the broad aspect comprises the unique combination of fractionally distilling and extractively distilling suitablel feed stock materials for the separation of individual hydrocarbon compounds as a continuous process in which relative purity of the solvent recycle is maintained.

What is claimed is: In a process for separating isoprene from a closely boiling mixture containing C monoolens,

y 1o withdrawing a bottoms fraction containing cyclopentadiene and dicyclopentadiene from the said third distillation yzone and combining this bottoms fraction with at least a portion C5 paraii'ins, isoprene and cyclopentadiene by fractional distillation in the presence of an acetone solvent in an extractive distillation zone in which the relatively saturated parains and monoolens are removed as distillate, the relatively less saturated isoprene and cyclopentadiene are removed as an intermediate fraction containing solvent, the remaining solvent is removed as a bottoms fraction containing a major proportion of acetone and dicyclopentadiene formed in the extractive distillation operation, and the said intermediate fraction is redlstilledto separate a distillate fraction of isoprene concentrate and a residual fraction high in acetone content and containing dicyclopentadiene formed in said redistillation step, the improved process for separating cyclopentadiene and dicyclopentadiene from said bottoms and residual fractions comprising returning the residual solvent fraction from said redistlllation step to an isoprene stripping stage of said extractive distillation zone, subjecting said isoprene concentrate to a second fractional distillation in a third distillation zone to recover puried isoprene distillate therefrom,

of the said bottoms solvent-dicyclopentadiene fraction removed from said rst extractive distillation zone and contacting these combined bottoms fractions with sunicient water to cause separation of a dilute aqueous acetone phase and -a hydrocarbon phase containing said cyclopentadiene and dicyclopentadiene polymer.

JOHN A. PATTERSON.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 2,250,925 Babcock July 29, 1941 2,361,493 Patterson c Oct. 31, 1944 2,370,530 Gage Feb. 27, 1945 2,371,342 Mayfield Mar. 13, 1945 2,372,668 Hachmuth Apr. 3, 1945 2,372,941 Evans et al. Apr. 3, 1945 2,377,049 Souders, Jr May 29, 1945 FOREIGN PATENTS Number Country Date 548,734 Great Britain O'ct. 22, 1942 

